U.S. patent number 4,255,515 [Application Number 05/959,592] was granted by the patent office on 1981-03-10 for photographic films.
This patent grant is currently assigned to Konishiroku Photo Industry Co., Ltd.. Invention is credited to Naoto Abe, Masao Ishihara, Masayoshi Mayama, Koichi Nagayasu, Toshiaki Shibue.
United States Patent |
4,255,515 |
Shibue , et al. |
March 10, 1981 |
Photographic films
Abstract
A photographic film which comprises (A) a support, having two
sides, (B) at least one light-sensitive emulsion layer on one side
of said support (A), and, (C) at least one layer containing a
compound represented by formula [I]and a hydrophobic polymer (first
layer) and at least one layer containing an antistatic agent
(second layer), said first and second layers being placed on the
other side of said support (A) and said first layer being placed
closer to said support (A) than said second layer: ##STR1##
wherein, R.sub.1 represents a carboxylic acid residue having from
12 to 24 carbon atoms and R.sub.2, R.sub.3 and R.sub.4 represent
independently hydrogen atoms or organic acid residues having from 1
to 24 carbon atoms.
Inventors: |
Shibue; Toshiaki (Hino,
JP), Nagayasu; Koichi (Hino, JP), Mayama;
Masayoshi (Hino, JP), Ishihara; Masao (Hino,
JP), Abe; Naoto (Hino, JP) |
Assignee: |
Konishiroku Photo Industry Co.,
Ltd. (Tokyo, JP)
|
Family
ID: |
15240846 |
Appl.
No.: |
05/959,592 |
Filed: |
November 13, 1978 |
Foreign Application Priority Data
|
|
|
|
|
Nov 19, 1977 [JP] |
|
|
52-139246 |
|
Current U.S.
Class: |
430/495.1;
430/527; 430/531; 430/533; 430/961 |
Current CPC
Class: |
G03C
1/85 (20130101); G03C 1/7614 (20130101); Y10S
430/162 (20130101) |
Current International
Class: |
G03C
1/85 (20060101); G03C 1/76 (20060101); G03C
001/78 () |
Field of
Search: |
;96/87A,5PL,67
;430/527,531,533,529,495,961 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Louie, Jr.; Won H.
Attorney, Agent or Firm: Frishauf, Holtz, Goodman &
Woodward
Claims
We claim:
1. A photographic film which comprises (A) a support having two
sides, (B) at least one light-sensitive silver halide emulsion
layer on one side of said support (A), and, (C), at least one layer
containing a compound represented by formula I and a hydrophobic
polymer (first layer) and at least one layer containing an
antistatic agent (second layer), said first and second layers being
placed on the other side of said support (A) and said first layer
being placed closer to said support (A) than said second layer:
##STR8## wherein, R.sub.1 represents a carboxylic acid residue
having from 12 to 24 carbon atoms and R.sub.2, R.sub.3 and R.sub.4
represent independently hydrogen atoms or organic acid residues
having from 1 to 24 carbon atoms.
2. The photographic film as claimed in claim 1, wherein R.sub.1,
R.sub.2 and R.sub.3 are straight chain carboxylic acid residues
having from 12 to 24 carbon atoms.
3. The photographic film as claimed in claim 2, wherein R.sub.4 is
a straight chain carboxylic acid residue having from 12 to 24
carbon atoms.
4. The photographic film as claimed in claim 1, in which the
compound having formula (I) is selected from the group consisting
of: ##STR9##
5. The photographic film as claimed in claim 1 or 2, wherein the
hydrophobic polymer is a cellulose derivative.
6. The photographic film as claimed in claim 1 or 4, wherein the
hydrophobic polymer is cellulose diacetate.
7. The photographic film as claimed in claim 1, wherein the
antistatic agent is a high molecular electrolyte.
8. The photographic film as claimed in claim 1 or 4, wherein the
second layer is formed by using a coating solvent which dissolves
substantially none of the first layer.
9. The photographic film as claimed in claim 6, wherein R.sub.4 is
a straight chain carboxylic acid residue having from 12 to 24
carbon atoms.
10. The photographic film as claimed in claim 8, wherein R.sub.4 is
a straight chain carboxylic acid residue having from 12 to 24
carbon atoms.
11. The photographic film as claimed in claim 9, wherein the
antistatic agent is a high molecular electrolyte.
12. The photographic film as claimed in claim 10, wherein the
antistatic agent is a high molecular electrolyte.
13. The photographic film as claimed in claim 10, wherein the
hydrophobic polymer is cellulose diacetate.
Description
The invention relates to light-sensitive photographic materials.
More particularly, it relates to photographic films having
antistatic reverse side layer with which the scratch-proof property
of the film has been improved.
A scratch mark may sometimes be generated on the surface of
photographic films, during exposing or treating of films such as
processing and printing, by the contact or friction of films with
apparatuses. The scratch mark tends to be generated on the reverse
side of films which may readily come into contact with apparatuses
and become severe cause of practical troubles upon printing and
projection.
Scratch marks may be generated during not only treating steps but
also manufacturing steps of films. Currently, it is required to
accelerate manufacturing and processing steps, and hence, it is
desired to obtain photographic films having scratch-proof reverse
side layers which can meet the requirement of the acceleration.
Heretofore, various attempts have been made to improve the
scratch-proof property of the reverse side layer of photographic
films. For example, a measure to improve the scratch-proof property
not only by increasing the mechanical strength of the reverse side
layer of photographic films but also by decreasing the sliding
friction of the reverse side layer has been proposed. However,
known photographic films containing a lubricant within the reverse
side layer lose most of or a part of the lubricant during
processing and lose the effect. This is significant when an
antistatic agent is dissolved during processing. Consequently,
scratch marks tend to be generated during subsequent
processing.
If too much of a lubricant is contained within the reverse side
layer, allowing for the loss of it, it will cause film transfer
trouble during manufacture called "overslipping trouble." Namely,
known photographic films having a slipping reverse side layer may
maintain the necessary slipping property and improve the
scratch-proof property for the period from the manufacture to some
step of use.
However, they can not maintain the necessary slipping property
before and after processing, unless there is provided a measure,
for example, to process them with a bath containing a lubricant
during processing.
It is, therefore, an object of the invention to provide
photographic films having an antistatic reverse side layer which
may exhibit an excellent scratch-proof property before and after
processing.
It is another object of the invention to provide photographic films
having the same or different slipping property before and after
processing so as to be suitable for respective processes and
operations.
It is still another object of the invention to provide photographic
films having reverse side layers capable of maintaining a
sufficient slipping property before and after processing, even if
there is no treatment thereof with a bath containing a lubricant at
the time of processing.
The inventors have found, after extensive investigations, that the
objects of the invention may be attained, in photographic films
having a light-sensitive emulsion layer on one side of a support
and other layers on the reverse side, by providing, as the reverse
side layers, (1) at least one layer comprising a compound
represented by the following formula (I) and a hydrophobic polymer
(first layer), and, (2) at least one layer comprising an antistatic
agent (second layer), such that the first layer is located closer
to the support than the second layer: ##STR2## In the above formula
[I], R.sub.1 represents a carboxylic acid residue having from 12 to
24 carbon atoms, and R.sub.2, R.sub.3 and R.sub.4 represent
independently hydrogen atoms or organic acid residues having from 1
to 24 carbon atoms.
As the carboxylic acid residue having from 12 to 24 carbon atoms
represented by R.sub.1 are mentioned, for example, residues derived
from saturated monocarboxylic acids such as lauric acid, palmitic
acid and stearic acid, unsaturated monocarboxylic acids such as
oleic acid, linolenic acid and linoleic acid, aromatic carboxylic
acids such as benzoic acid, naphthalenecarboxylic acid and phthalic
acid, and carboxylic acids in which hydrogen atom of the
above-mentioned carboxylic acid may substituted with a hydroxy
group or a halogen atom such as fluorine, chlorine and bromine. As
the organic acid residues having from 1 to 24 carbon atoms
represented by R.sub.2, R.sub.3 and R.sub.4 are mentioned, for
example, carboxylic acid residues represented by R.sub.1, and
ketocarboxylic acid residues derived from acetoacetic acid,
p-acetylbenzoic acid, benzoylacetic acid, or the like.
Among the compounds of formula [I] to be used in the invention,
those in which R.sub.2 and R.sub.3 are straight chain carboxylic
acid residues having from 12 to 24 carbon atoms are preferable.
More preferable are those, in addition to above, in which R.sub.4
is a straight chain carboxylic acid residue having from 12 to 24
carbon atoms.
Compounds of formula [I] to be used in the invention may be
employed alone or together.
Representative examples of compounds of formula [I] to be used in
the invention include: ##STR3##
Examples of preparation of compounds represented by formula [I] are
given below.
Preparation 1
(Illustrated Compound No. 1)
Into a 200 ml. round bottom, short neck flask fitted with an
esterification tube and a cooler were placed 3.4 g. of
pentaerythritol, 14.2 g. of stearic acid, 0.5 g. of
p-toluenesulfonic acid and 100 ml. of toluene. The
transesterification was performed by refluxing the mixture at about
120.degree. C. of external temperature, while removing water formed
in situ.
After completion of removal of the water, the reaction mixture was
cooled and washed several times in a separating funnel with water
to remove the p-toluenesulfonic acid. A waxy substance thus
obtained was washed several times with methanol to remove the
unreacted materials, giving the desired product, pentaerythritol
distearate. The results of elementary and NMR analyses revealed
that the substance had the desired structure.
Preparation 2
(Illustrated Compound No. 6)
Into a 300 ml. round bottom, short neck flask fitted with an
esterification tube and a cooler were placed 6.8 g. of
pentaerythritol, 64.1 g. of palmitic acid, 1.0 g. of
p-toluenesulfonic acid and 150 g. of toluene. The
transesterification was performed by refluxing the mixture at about
130.degree. C. of external temperature, while removing water formed
in situ.
After completion of removal of the water, the reaction mixture was
washed several times in a separating funnel with water to remove
the p-toluenesulfonic acid. A waxy substance thus obtained was
purified to give the desired pentaerythritol tetrapalmitate, which
was confirmed to have an aimed structure by elementary and NMR
analyses.
Preparation 3
(Illustrated Compound No. 9)
Into a 200 ml. round bottom, short neck flask fitted with an
esterification tube and a cooler were placed 3.4 g. of
pentaerythritol, 16.0 g. of palmitic acid, 14.2 g. of myristic
acid, 0.5 g. of p-toluenesulfonic acid and 100 ml. of benzene. The
transesterification was performed by refluxing the mixture at about
110.degree. C. of external temperature, while removing water formed
in situ. After completion of removal of the water, the reaction
mixture was cooled and washed several times in a separating funnel
with water to remove the p-toluenesulfonic acid. A waxy substance
thus obtained was washed several times with methanol to remove the
unreacted materials, giving the aimed pentaerythritol dipalmitate
dimyristate. The chemical structure of the substance was confirmed
by elementary and NMR analyses.
Hydrophobic polymers to be used in the invention may be coated and
dried in the form of a solution or dispersion. They are preferably
those which are insoluble in an acidic, alkaline or neutral
solution such as processing baths (e.g. developing or fixing
solution or washing water etc.). As the hydrophobic polymer used in
the invention are mentioned, for example, cellulose derivatives
such as cellulose diacetate, cellulose triacetate, cellulose
acetate butylate, cellulose nitrate and ethylcellulose; polyvinyl
acetals; vinyl chloride/vinylidene chloride copolymers; vinyl
chloride/acrylonitrile copolymers; acrylic acid ester/vinyl
chloride/vinyl acetate copolymers; vinylidene chloride/methyl
acrylate/acrylic acid copolymers; or the like. Thereof, preferable
for the hydrophobic polymers are cellulose derivatives, inter alia,
cellulose diacetate.
In order to provide a layer comprising a compound of formula [I] of
the invention and a hydrophobic polymer (hereinafter referred to as
first layer), a compound of formula [I] and a hydrophobic polymer
are dissolved in a suitable solvent to make a coating solution,
which is coated on a support and dried by a conventional
method.
The concentration of the compound of formula [I] ranges preferably
from 0.01 to 1 g., more preferably from 0.05 to 0.4 g. per 100 ml.
of the solvent. The mixing ratio of the hydrophobic polymer to the
compound of formula [I] ranges preferably from 1/2 to 4, more
preferably from 1 to 2 by weight, based on one part of the compound
of formula [I].
The amount of the compound of formula [I] to be coated is from 3 to
300 mg./m.sup.2 of a photographic film.
As the solvent to be used, there is no specific limitation as to
the nature and are mentioned, for example, acetone, ethyl acetate,
methylene chloride, ethylene dichloride, trichloroethylene,
benzene, or the like. They may be optionally selected and used
alone or together.
The coating solution may be coated on a support by a conventional
method such as dip-coating, roller-coating and spray-coating and
thereafter dried by a usual method.
The first layer may further contain various additives such as
matting agent which may be necessary depending on the usage of
photographic films.
As the antistatic agent to be used in the invention, those which
provide a good electroconductivity and have a superior film-coating
property by themselves, or when used in combination with a suitable
binder, such as a polymer electrolyte are effectively used.
Examples of such antistatic agents may be copolymerization salts of
styrene with styreneundecanoic acid, disclosed in U.S. Pat. No.
3,333,679; maleic acid or maleinimide resins, disclosed in U.S.
Pat. No. 2,279,410; alkali metal salts of alkylarylpolyether
sulfonic acids and of carboxylic acid polymers, disclosed in U.S.
Pat. No. 3,525,621; alkali metal salts of polycarboxylic acids,
disclosed in U.S. Pat. No. 3,630,742; polystyrenesulfonic acids,
disclosed in U.S. Pat. No. 2,735,841; quaternary salts of
polyvinylpyridine, disclosed in U.S. Pat. Nos. 2,787,834 and
3,072,484; polyquaternary alkylaminoacrylate, disclosed in U.S.
Pat. No. 2,882,152; anionic polymer of maleic acid derivative,
ionen type polymer, copolymer of a pendant type quarternary
ammonium salt monomer and a hydrophobic monomer, copolymer of a
pendant type quarternary ammonium salt monomer and a monomer
containing fluorine disclosed in Japanese Patent Publication
Specification Nos. 46-24159, 50-54672 and 50-94053, as laid open to
public inspection, and Japanese Patent Application Specification
No. 51-45458 respectively. Thereof, those disclosed in Japanese
Patent Publication Specification Nos. 46-29159, 50-54672 and
50-94053, as laid open to public inspection, and Japanese Patent
Application Specification No. 51-45458 are advantageously employed.
It is preferable that a layer containing an antistatic agent of the
invention (hereinafter referred to as second layer) is provided
adjacent to and upper side of the aforementioned first layer.
In order to attain this an antistatic agent is dissolved in a
suitable solvent to make a solution, and where required, it is
jointly used with a binder to make a coating solution, which is
coated and dried on the surface of the first layer on the support.
As the solvent for the antistatic agent, there may be employed
methanol, ethanol and acetone, besides water, and they may be
employed together. The coating solution may be coated on the first
layer of the support by a conventional method such as dip-coating,
roller-coating and spray-coating, and thereafter dried according to
a usual method.
There is no specific limitation as to concentration of the
antistatic agent in the coating solution; but it is preferable from
the viewpoints of easiness of coating and drying that the
antistatic agent is contained in an amount of from 0.01 to 10% by
weight. The amount of antistatic agent to be coated is from 3 to
300 mg. per square meter, in general, of a photographic film, by
which a satisfactory antistatic effect may be obtained. As
previously mentioned, any solvent composition may be used for the
coating solution of the second layer.
However, if the solvent system permeates the first layer
excessively, it will impair the transparency after the coating of
second layer. In order to avoid this, more than 5%, preferably from
10 to 30% of water is contained in the solvent. When more water is
used, the resulting coating solution may be coated together with a
coating aid such as surface active agent. The compound of formula
[I] within the first layer may be dissolved, depending on the
amount thereof contained, to affect the slipped property of the
second layer, therefore in this case a slipping agent or an
antislipping agent may be added into the second layer so as to
adjust the slipping property of the second layer. The slipping
property may also be adjusted by changing the solvent composition,
particularly by changing the amount of water in the coating
solution of the second layer. The second layer may contain a
matting agent like silicon dioxide, depending on the usage. There
may be further provided various layers on the second layer such as
a slipping layer, a matting layer containing silicon dioxide
particles, or a layer containing an anionic material or other
organic compounds. The scratch-proof property of films thus
obtained has been improved and the electrification caused by
friction or exfoliation may be prevented. Moreover, degradation of
photographic characteristics such as reduction of sensitivity,
increase of fog and change of gamma value may also be
prevented.
The present invention may be applied to any support for a
photographic material. Examples of the support is a
cellulosetriacetate, polyethyleneterephthalate film or luminate
paper coated with polycarbonate, polystyrene, polyolefin or
polyethylene.
A light-sensitive emulsion layer contains silver halide
light-sensitive photographic emulsion.
The invention is further explained by the following examples which
by no means restrict the scope of the invention.
EXAMPLE 1
On the surface of a cellulose acetate film was coated a solution
(A) consisting of 4 g. of cellulose diacetate, 3 g. of illustrated
compound No. 2, 400 ml. of acetone, 300 ml. of methylene chloride
and 300 ml. of ethyl acetate in an amount of 30 ml./m.sup.2 and
dried to have the first layer. Thereon, was coated a solution (B)
consisting of 3 g of styrene/maleic acid p-aminobenzoic acid sodium
salt copolymer, 0.1 g. of sodium cetylsulfate, 650 ml. of methanol,
250 ml. of acetone and 100 ml. of water in an amount of 20
ml./m.sup.2 and dried to form the second layer, thus giving a
cellulose triacetate film having the first and second layers and
bearing adequate slipping and antistatic properties. Then, the
other side of the film was undercoated to form a subbing layer,
upon which a silver halide emulsion was coated and dried to give a
photographic film [I] according to the invention. The results of a
series of actual performance, namely exposing with a camera,
processing and printing revealed that almost neither static marks
nor scratch marks were observed on a print and that no degradation
of photographic characteristics was observed as well.
For comparison, a photographic film [II] was obtained by coating a
solution (C) containing none of the above-mentioned compound No. 2,
in place of solution (A), in an amount of 30 ml./m.sup.2, as well
as a photographic film [III] containing the second layer only were
prepared and processed in the same way as in the photographic film
[I]. A photographic film [IV] was obtained in the same way as the
film [I] except only that the first layer and the second layer were
exchanged. A considerable number of scratch marks were observed on
prints obtained from the photographic films [II], [III] and
[IV].
The values of static friction coefficient (.mu.s) and kinetic
friction coefficient (.mu.k) of the specimens against a
styrene/butadiene board are shown in Table 1.
TABLE 1 ______________________________________ Film .mu.s .mu.k
______________________________________ Film [I] before processing
0.45 0.38 after processing 0.34 0.28 Film [II] before processing
0.48 0.42 after processing 0.46 0.45 Film [III] before processing
0.42 0.43 after processing 0.46 0.44 Film [IV] before processing
0.32 0.27 after processing 0.45 0.44
______________________________________
EXAMPLE 2
On the surface of a biaxially stretched, crystallized polyethylene
terephthalate was coated a solution (D) having the following
composition in an amount of 20 ml./m.sup.2 and dried to having the
first layer:
______________________________________ Cellulose triacetate 3 g.
tertiary copolymer consisting of vinylidene chloride, methyl
acrylate 1 g. and acrylic acid (65:35:2, by weight) illustrated
compound No. 8 1.5 g. ethylene dichloride 650 ml. methylene
dichloride 200 ml. phenol 150 ml.
______________________________________
Thereon, was coated solution (E) having the following composition
in an amount of 20 ml./m.sup.2 and dried, forming the second
layer:
______________________________________ ##STR4## 5 g. resorcinol 50
g. methanol 300 ml. acetone 500 ml. water 200 ml.
______________________________________
The reverse side of the film was undercoated to make a subbing
layer, upon which a silver halide emulsion was coated and dried,
giving a photographic film [V] according to the invention.
The results of a series of actual performance, namely photographing
with a camera, developing and printing revealed that almost neither
static marks nor scratch marks were observed on a print and that no
degradation of photographic characteristics was observed as
well.
For comparison, a photographic film [VI] having a biaxially
stretched, crystallized polyethylene terephthalate film was
obtained by coating and drying a solution (F) containing no
above-mentioned illustrated compound No. 8, in place of solution
(D), in an amount of 20 ml./m.sup.2, as well as a photographic film
[VII] having containing the second layer only were prepared and
processed in the same way as in the photographic film [V].
Considerable number of scratch marks were observed on prints
obtained from the photographic films [VI] and [VII].
The values of .mu.s and .mu.k of the specimens against a
styrene/butadiene board are indicated in Table 2.
TABLE 2. ______________________________________ Film .mu.s .mu.k
______________________________________ Film [V] before processing
0.45 0.48 after processing 0.31 0.32 Film [VI] before processing
0.47 0.42 after processing 0.44 0.45 Film [VII] before processing
0.42 0.38 after processing 0.43 0.46
______________________________________
EXAMPLE 3
On a surface of a cellulose triacetate film was coated a solution
(G) having the following composition in an amount of 20 ml./m.sup.2
and dried:
______________________________________ cellulose diacetate 3 g.
illustrated compound No. 9 2 g. silicon dioxide particles 1 g.
acetone 550 ml. ethylene dichloride 250 ml. methylene dichloride
200 ml. ______________________________________
Thereon, was coated a solution (H) having the following composition
in an amount of 20 ml./m.sup.2 and dried, forming the second layer
and giving an antistatic triacetate film having the first and
second layers:
______________________________________ ##STR5## 1 g. triethylamine
salt of stearylphosphoric 0.1 g. acid acidic ester acetone 500 ml.
methanol 250 ml. water 350 ml.
______________________________________
The reverse side of the film was undercoated to make a subbing
layer, upon which a silver halide emulsion was further coated and
dried, giving a photographic film [VIII] according to the
invention.
The results of a series of actual performance, namely photographing
with a camera, developing and printing revealed that almost neither
static marks nor scratches were observed on a print and that no
degradation of photographic characteristics was observed as
well.
For comparison, a photographic film [IX] was obtained by coating
and drying a solution (H) containing no above-mentioned compound
No. 9, in place of dispersion (G), in an amount of 20 ml./m.sup.2.
While a photographic film [X] containing the second layer only were
prepared and processed in the same way as in the photographic film
[VIII]. Considerable number of scratch marks were observed on
prints obtained from the photographic films [IX] and [X].
The values of .mu.s and .mu.k of the specimens against a
styrene/butadiene board are indicated in Table 3.
TABLE 3. ______________________________________ Film .mu.s .mu.k
______________________________________ Film [VIII] before
processing 0.31 0.32 after processing 0.35 0.30 Film [IX] before
processing 0.43 0.42 after processing 0.47 0.45 Film [X] before
processing 0.37 0.35 after processing 0.96 0.45
______________________________________
EXAMPLE 4
On a surface of a cellulose triacetate film was coated a solution
(I) having the following composition in an amount of 20 ml./m.sup.2
and dried:
______________________________________ cellulose diacetate 2 g.
illustrated compound No. 13 2 g. acetone 400 ml. methylenchloride
300 ml. methanol 300 ml. ______________________________________
Then the following solution (J) was coated on in an amount of 20
ml./m.sup.2 and dried:
______________________________________ ##STR6## n.sub.1 :n.sub.2 =
50:50 2 g. methanol 650 ml. acetone 200 ml. water 150 ml.
______________________________________
The reverse side of the film was undercoated to make a subbing
layer, on which a silver halide emulsion was further coated and
dried to obtain a photographic film [X] according to this
invention.
For comparison, a photographic film [XI] was obtained in the same
manner except that coating the solutions (I) and (J) were replaced
to a coating solution having the following composition (K):
______________________________________ ##STR7## 2 g. cellulose
diacetate 2 g. illustrated compound No. 13 2 g. acetone 400 ml.
methylenchloride 300 ml. methanol 300 ml.
______________________________________
It was coated in an amount of 20 ml./m.sup.2.
Both films were processed in the same way as in Example 1.
Considerable number of scratch marks were observed on a print
obtained from the photographic film [XI].
The values of .mu.s and .mu.k of the photographic films against a
styrene/butadiene board are shown in Table 4.
TABLE 4. ______________________________________ Film .mu.s .mu.k
______________________________________ Film [XI] before processing
0.38 0.37 after processing 0.30 0.26 Film [XII] before processing
0.31 0.29 after processing 0.47 0.46
______________________________________
* * * * *